Jump to main content
Jump to site search


Pentavalent Phosphorus as a Unique Phosphorus Donor in POCl3 Homodimer and POCl3-H2O Heterodimer: Matrix Isolation Infrared Spectroscopic and Computational Studies

Abstract

Phosphorus, an important element among the pnicogen group opens up avenues for experimental and computational explorations of its interaction in varieties of compounds. Although experimental proof for trivalent phosphorus bonding is limited and is growing with time, phosphorus bonding with pentavalent phosphorus has been a long sought after interaction both computationally and experimentally. In the present work, for the first time we have provided unambiguous experimental evidence for the pentavalent phosphorus bonding interaction by exploiting phosphoryl chloride (POCl3) prototype under isolated conditions at low temperatures. POCl3 dimer and higher aggregates can be set as a unique example possessing pentavalent phosphorus bonding with a competing halogen bonding interaction. POCl3-H2O heterodimer is another interesting system, stabilized through multiple phosphorus and hydrogen bonded interactions. Using matrix isolation infrared spectroscopy, POCl3 homodimer and POCl3-H2O heterodimer were characterized and the structures were elucidated employing ab initio and DFT methods. The multifaceted interactions in POCl3 paradigm were investigated using Natural Bond Orbital, Energy Decomposition and Electrostatic Potential Mapping analyses.

Back to tab navigation

Supplementary files

Publication details

The article was received on 21 Jun 2018, accepted on 27 Jul 2018 and first published on 31 Jul 2018


Article type: Paper
DOI: 10.1039/C8CP03937B
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
  •   Request permissions

    Pentavalent Phosphorus as a Unique Phosphorus Donor in POCl3 Homodimer and POCl3-H2O Heterodimer: Matrix Isolation Infrared Spectroscopic and Computational Studies

    P.K. Sruthi, N. Ramanathan, S. Sarkar and S. Kalyanasundaram, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP03937B

Search articles by author

Spotlight

Advertisements